Paraffin wax chlorination process



June 14,1960 J. w. JENNEY L 2,941,013

PARAFFIN WAX CHLORINATION PROCESS Filed Nov. 6, 195a JOHN W. JENNEYRICHARD C. RAHN BY fiutJ/M.

ATTORNEY ville, Ohio, assignors to Diamond Alkali Company,

Cleveland, Ohio, a corporation of Delaware Filed Nov. 6, 1958, Ser. No.772,656

2 Claims. (Cl. 260-660) This invention relates to-chlorinated parafiinwaxes. It relates more particularly to a process for preparing liquidchlorinated parafiin waxes having improved um form light color and goodheat stability.

This is a continuation-impart of our co-pending application Ser. No.620,255, now abandoned.

The conventional substitution chlorination of paraffin waxes is wellknown in the art. The procedure for chlorinating paraffin waxes usuallyconsists of passing chlorine gas through a body of molten wax until itreacts with the desired amount of chlorine. According to this procedure,chlorinated paraifin waxes are produced ranging in chlorine content byweight-from as low as 10% up to 70% and higher. The color of thechlorinated waxes produced by this process ranges from red to dark brownto black depending on the chlorine content of the final product.

Chlorinated waxes find many uses in improving and modifying a widevariety of materials. Accordingly, it is desirable in many instances toproduce a chlorinated wax of a uniform light color in order to meet thespecifications of the user.

This invention has as an object, therefore, the preparation ofchlorinated paraffin waxes of improved color characteristics. A furtherobject of this invention is the prep aration of liquid chlorinatedparafiin waxes of improved uniform light color and good heat stability.

In accordance with the foregoing objects, and others to become apparenthereinafter, this invention relates to an improvement in a process forproducing a liquid chlorinated'parafiinby contacting a molten parafinicsubstance with chlorine, which comprises the steps of contacting amolten body of said substance with gaseous chlorine at a chlorinationtemperature of below about 90 C., maintaining said temperature until "upto about 33% of the desired chlorination has been obtained, and

air at P t Q Patented June 14, 1960.

. 2 v this invention are those containing long-chain parailinicmolecules, preferably from 18 to 28 carbon atoms. Paraffin waxes of thistype ordinarily have a melting point range of about 45 to 60 C. Itshould be understood, however, that parafiin waxes having higher orlower melting point ranges can also be employed." The preferred meltingpoint range of the paraffin waxes to be employed in the process of thisinvention is about 47 to 54 C. Generally, such parafiin waxes consist ofstraightchain hydrocarbon molecules, although the material can alsocontain minor amounts of branch-chain or other molecular configurations.

In chlorinating a molten body of paraffin wax, it is not consideredessential to employ a chlorine gas of 100% purity. Thus, chlorine gasfrom electrolytic cells, i.e., from the electrolysisof brine, can besuitably em ployed. Such chlorine gas can consist of, for example, 90%or more of chlorine-with the rest of the material consisting of oxygen,hydrogen, carbondioxide and nitrogen, the latter being the majorimpurity. It is found that a gaseous material comprising 90 to 95%chlorine gives desirable results in paraflin wax chlorination reactions.

In the preferred embodiment of this inventon, a liquid chlorinatedparafiin wax of improved uniform light color and heat stability isprepared by contacting a molten body 7 of paraflin wax with gaseouschlorine in a reaction zone,

continuing said chlorination at a temperature below about 100 C. until'the desired amount of chlorine has reacted. By the process of thisinvention, it is found that liquid chlorinated p'arafiins can beprepared possessing improved uniform light color characteristics andgood heatstabiliy I As indicated briefly above, this invention relatesto a process for producing liquid chlorinated'parafiins by chlorinatinga parafiinc substance at optimum temperatures to produce a liquidproduct that possesses a 'uni form and desirable color. The termparaffinic substance is intended to include paraflin waxes and oilsderived from petroleum distillates' of mineral oils of the mixedandparaflin base type. Processes for'producing such waxes and oils are wellknown in the art and it is not considered necessary here to describetheir preparation. Such products are available commercially.Hereinafter, reference will be made only to paraifin waxes, it beingunderstood that the invention also includes paraflin oils adaptable tothis process. V

Preferred parafiin waxes employed in the process of said chlorine gasintroduced under pressure, and the reaction carried out at a temperatureof below about 90 C. for a period of time sufiicient to obtain up toabout 33% of the chlorination, and thereafter continuing thechlorination .below a temperature of about 100 C. until the desiredamount of chlorine has reacted.

In the preferred embodiment of this invention, the amount of chlorinethat can be chemically introduced into the parafiin wax ranges from 30to 50% by weight of the wax. A more preferred amount .of chlorine to bechemically introduced into the wax is about 40% by weight of the wax.

The products of this invention are liquid and differ in regard tochemical and physical properties, for example, viscosity and degree ofchlorination, as will be un-.

derstood by those skilled in the art. Excellent results in regard tocolor and heat stability of the liquid chlori-. nated materials areobtained with paraifin waxes chlorinated to about-40% by weight. i Inthe process of this invention, gaseous chlorine is; preferablyintroduced at a pressure of from 10 to 25 lbs. per square inch tocontact a body of molten paraflin Wax. The contact is carried out for aprolonged periodof time, such time depending, of course, onthe amount ofchlorineto be introduced into the wax, the pressure of thechlorine,.-and the temperature ofthe reaction. 5 In order to'faciltatethe control of the reaction tem. perature, i.e., below 90 C., chlorineis metered to the reaction zone in an amount calculated to preventan-excessive rise of temperature, since as is well known, the

reaction of paraflin wax and chlorine is exothermic- Cooling means areconveniently provided in the reaction vessel to control the temperaturewithin the desired limits. I

The time required to cause chlorination will vary with the degree oramount of chlorination desired. It isfound.

that for producing a parafiin wax of about 40% by weight chemicallycombined chlorine, the time required is inthe order of from 50 to hourswhen cmploying'the reaction conditions of this invention. This time, ofcourse, can also vary with the efiiciency of the chlorinating apparatusand the temperatures employed in the reaction.

The chlorination temperatm'esemployed for the first step in thepreferred embodiment offthis invention are about from 60 to C. Ingeneral, the lower the temperature, the better the result insofar ascolor is concerned-and in consequence of this, an optimum temperaturefor -superior results is 85 C. Accordingly, a

temperatures can be used but would require reductiorl inv'chlor'ine feedr-ate andffhus a longer batch temperatures higher than 90 C.areeinployd, thejprodg not is otf colon "-It should be 'unde'rsto'c'ji'however, that this'ofi mares product is suitable foe 'many uses whejreother-properties of the material are more important than its colorfl'lhe lower temperature ofthe' chloririation is limited, of coursefltothe melting point of the'parafiin' Superior results are obtainedbyfcontacting gaseous chlorine with -molten-paraflin wakluntil about 33%of the chlorine desired to be iritroduced-intoathe wax has reactedand-the terrip'erature 'is kepti atiabout' 8513 The chlorination canthereafterbecontinued at slightly higher temperatures if desired, i'.e., to speedup the batch cycle, but it is d'esirable to keepsuch'temperamresbelow "about 1 C. inasmuch as the color of-the finalproduct canbe adversely afiected ifhigher temperatures are'used. "Inorder-that the invention may be morefully under-- stood, 'r fer'enee'ismade to the accompanying drawing illustrating a diagrammatic view of anapparatus for carrying out the process according to the preferredprocedure deseribed above. r

lined vessel which is proyidedwith a cooling jacket (not shown)surrounding thevessel. .The vessel 15 Provided with line 2 at the bottomfor withdrawingthejconterrts therefrom and line '3 to circulatethemolten' material to reaction zone 6 wherethe major part'o'f thereaction of chlorine with wax-is reflected; Chlorinegas is introducedunder-pressure by line 4 'andjlifts the rrrolten wax through line 5 toreaction zone 6n The contents from reaction zone 6 are-conveyed to thetop of the vessel 1 by' line 7.-1 i Gaseous :rproducts from the reactionsuch-as chlorine and hydrogen chloride are taken from the 'top 'of -the-reactor by line "8 for: recovery as islwell known inthe art. Numeral10indicates astorageivesfsel for parafiin waxand can be provided withheating 7 means for melting the wax; "The wax can be introduced fromstoragevesel10"to 'glasslinedvesselll by line 11 V ga'seouschlorine at apressureof from l'O-toj25 lb per square merrier dine 'The lchlorine'pressuref'is sufficient-tofliftqand circulate the 'moltenfwaxto thereactionzoneandfback to the vessel 1. T-he, temperature lined ve'ssel bycooling means, e.'g., a' water jacket,'and

by regulatingithe chlorine 'fiow into thereactionzone 6! 7 l ke chlorineflowinto reactor 6 cannot be dropped below 7 that necessary Jtojiliftandcirculate" the molten back i: (If jdesired, during chlorination of themolten parafiin wax, the temperature in vessel 1 can bemaintainedat aslightly highertemperature,-i.e., about 90 C., but not 7 7 above, sincea :higher temperature can aficct 'the color or the finished product. aIf thezwmolten lpar aflin'wax "in Y lcl atapteniperature near 90 C; itis des able :that the tempera'ture in the reaction zone' d thetemperature of 85 C. is preferred, although lower 7 hekept atabout 85 C.inorder not possess a good uniform light color. Good results that thefinished pro'dare obtained if the temperature in the lines are kept atabout 84-85 C. in line '3 and about 85 Co in lme 7. By-products fromthereaction, suchas'chlo'rine and hydrogen'chloride, are taken by line8, processed to recover chlorine and hydrogen-chloride, 'and'rdisposedof in any appropriate manner. The molten chlorlnated parafiin wax after:being te's'tedfto ileter'niine its' chlorine content is withdrawnhydine2 irit contain the-desired amount of chemically combined and treated' 1na separate area (not shown.) to; remove undrssolved chlorine or hydrogenchloride, such re air blowing;

mixture at a temperature ofabou't 8 5 C. {ii-om 2-5to 33%yof the desiredchlorination has been obtained.

The following examples will serve "to-illustrate the process of theinvention when tcarried aout m a commercial apparatus such as describedin the drawing. 7

Example I To a zglassdined vesselofapproximately 15.80 :gallon aboveitsfmelting'point. Chlorinegasgata pressure'ot V between '10 to25,;lbs1iper square inchlis introduced :mto

line 5 and metered at approximately .200 'lbs. perhour for'aperiodoftapproximately ,20 hours. During this time, the temperature-"in "thereactor is maintained. :be-

desired. The "chlorine 'feed after this periodis zthen;

increased to about :250ilbs.,per.hour and the reaction is continuedqforitahout r an additional fidhours. :During this "time, ther'eactionitemperaturefis" 90 95tC;1Ihe

, I a I total reactionitimezisaboutioo'hoursandr atithe end of s-Inthedrawing, numeral l-represents generally a glassthis period the paraffinwax, is chlorinated to anmitent of40%' ibyweiglr t chemically combinedchlorine;-

' Theichlorinated paraflin waxgfrom Example 1 has a V colorfindexofgfrom 1' to Zonthe Gardner Color Seale (HFA. Gardner, iPhysicalfandChemica'l Examination' of of-thewaxfis maintainedat about8590.,in'theg'las'sr ntroducedrat a'zpressure qfzaboutll, F V inch'andin-an amount on muraso lb perzhour @to="cons 3 t}! about J-SQQ 1-1138 1of-rmolteniwax. 68'

Paints, varnishes, Lacquers, and Colors,iNinthredition, Washington'Instimte'of Paint an'jd varnishf'iiesearch, '1 939) The product is ofmedium to low viscosity and is a liquid 'zof 'clear light amber colorhaving heat stability and containing 140% by weight chemically cornlizedby'additives for-a long/storage; life. r

' cr mp 1r;

bined chlorine; 'If desired, this productcanbe stabifa;sitar-merasasassi ns-nearede ults ofhisainventicn, a molten :paraffihwaxfis ehl esteem. cordingtotheiqllowing procedur ohlorinel is ?5carried out ateatemperature-nfgaho 2 Qt t:the::endiof :tliei reactinjp'eriod, thepmd;

r ct cohtai l ig' fi% hyweight che 'callyzcombinedichlol ipe iexaminedsan f nd r 'nranyzcoinmerciai and consequently,- objectionable:r

uses: This chlorinated paraffinwajir is foundP'toLa 'haVeea color ofironi 4' too on the idiicr; .GolorEScale. The reason tor-the offcotor'jot :productfwlrenzthe reaction -is carried out :at temperaturesiabove fGigiS not completely understood; l-lowever it has been :estab-;-'lishedrthat ,by holding' the temperaturez'atbelowaflf gC;andpre'fera'blyat 85 C.', untilabout 3 3% .ofjthe desir d 'r'eactionhasoccurred andthereafter raisingthetemperar: ture to abou tj Q if desired;there isfobtainedaclear light color liquid chlorinated'wax which is anim raved liquid chlorinated waxes of this invention can also be used infinishing fabrics, as flame retardant compositions, and are compatiblewith synthetic rubbers and the like to help maintain flame and chemicalresistance in such stocks. Other uses will be apparent to those skilledin the art.

The advantages to be realized by the process of this invention are: Achlorinated liquid parafiin wax can be produced possessing uniform lightcolor characteristics and good heat stability; the process is simple andthe conditions are easily controlled.

Although this invention has been described with specific reference tothe preparation of liquid chlorinated paraifin waxes of about 40% byweight of chlorine, the process is applicable to the production ofchlorinated waxes of higher or lower chlorine content.

Accordingly, it is intended to cover all modifications of the inventionthat fall within the spirit of the invention and the scope of theappended claims.

What is claimed is:

1. In a process for producing a chlorinated paraflin wax containingabout 40% by weight of chemically combined chlorine, by contacting amolten body of paraffin wax with gaseous chlorine, the improvement whichcorn prises the steps of contacting said molten body of paraflin waxwith gaseous chlorine at a chlorination temperature between about to C.,in the absence of a solvent,

References Cited in the file of this patent UNITED STATES PATENTS1,129,165 Buchner Feb. 23, 1915 1,953,286 Barth Apr. 3, 1934 2,189,924Pier et al Feb. 13, 194

2,214,877 Clark Sept. 17, 1940 FOREIGN PATENTS 199,073 Great BritainJune 18, 1923

1. IN A PROCESS FOR PRODUCING A CHLORINATED PARAFFIN WAX CONTAININGABOUT 40% BY WEIGHT OF CHEMICALLY COMBINED CHLORINE, BY CONTACTING AMOLTEN BODY OF PARAFFIN WAX WITH GASEOUS CHLORINE, THE IMPROVEMENT WHICHCOMPRISES THE STEPS OF CONTACTING SAID MOLTEN BODY OF PARAFFIN WAX WITHGASEOUS CHLORINE AT A CHLORINATION TEMPERATURE BETWEEN ABOUT 60 TO90*C., IN THE ABSENCE OF A SOLVENT, MAINTAINING SAID TEMPERATURE UNTILUP TO ABOUT 33% OF THE DESIRED CHLORINATION HAS BEEN OBTAINED, ANDCONTINUING SAID REACTION AT A TEMPERATURE OF BELOW ABOUT 100*C. UNTILSUFFICIENT CHLORINE HAS REACTED TO PRODUCE A CHLORINATED PARAFFIN WAXCONTAINING ABOUT 40% BY WEIGHT OF CHEMICALLY COMBINED CHLORINE.